Electrochemical treatments

Electrochemical treatments of wastewaters have not received great attention so far

because of the need of large capital investments and expensive electricity supply.

The electrochemical technologies are in a situation that they are not only

comparable with other technologies in terms of costs, but they also are more

efficient and more compact. In some cases, the electrochemical technologies may

be an essential step that cannot be neglected in treating wastewaters containing

refractory pollutants. In this review, three major electrochemical treatment

technologies including electro coagulation (EC), electro flotation (EF) and electro

deposition are studied.

Electro coagulation

Electro coagulation (EC) is a simple and productive technology used in wastewater

treatment industries. It was never accepted as a reliable method due to its poor

systematic reactor design and problems of electrode reliability. Recently, EC

became known as a small-scale wastewater treatment method with improved

technical strategies. A wide variety of disturbing pollutants is removed by

electrolysis.

EC with aluminum and iron electrodes was first patented in the United States in

1909. The whole EC process was conducted by applying a low electric current to
the waste solution. In the simplest form, the EC reactor is an electrolytic cell which

has one anode and one cathode which are commonly known as sacrificial

electrodes. These electrodes may be made of similar or different kinds of materials.

Iron and aluminum are among the most popular materials. At the beginning,

pollutants such as heavy metal ions are retained in the wastewater by their surface

electrical charges or hydrogen bond. After introducing the electric field, the

electrostatic charges holding the suspended or emulsified pollutants together are

neutralized and they will then be coagulated from the aqueous phase.

Heavy metal particles bond together like small magnets to form

a mass that is called sludge or floc. The flocs produced through EC compared with

those of other techniques are large with less bound water and are more stable. The

advantage is that these flocs can easily be removed by further processing like

filtration which sometimes is cost-intensive but easily operated. The procedure can

be summarized as follows:

– Anode dissolution;

– OH– and H2 generation at the cathode;

– Electrolytic reactions at electrode surfaces;

– Coagulant adsorption on colloidal pollutants;

– Colloids removal by sedimentation or flotation.

For Al electrodes, the main reactions include:

 Anode: Al⇌ Al3+ +3e--------------- (1)

Cathode: 3H2O + 3e- ⇌ 3/2H2 + 3OH---------- (2)

Al3+ and OH– ions formed at the electrode surfaces react in the wastewater:

Al3+ +3OH- ⇌ Al(OH)3 ---------------- (3)

Al(OH)3 acts as adsorbent and/or trap to separate heavy metal ions. Fig shows the

SEM (scanning electron microscopy) image of metallic sludge for the removal of

Mn2+ and Co2+ ions from aqueous solutions using EC with Al electrodes. Fig

shows the SEM images of the anode after Electro coagulation using AC

(alternative current) and DC (direct current) for the removal of cadmium from

water using zinc as anode and cathode. In Fig., the SEM images of

Fig
SEM image of metallic sludge for the removal of Mn2+ and Co2+ ions from aqueous

solutions using EC with Al electrodes

Fig

SEM images of the anode after electro coagulation (a) by AC and (b) by DC for

the removal of cadmium from water using zinc as anode and cathode
SEM images of the Al alloy anode (a) before and (b) after EC process to remove

chromium

the Al alloy anode before and after the EC process to remove chromium are

presented. The results showed that the optimum removal efficiency of 98.2% was

achieved using an Al alloy anode at a current density of 0.2Adm–2 at a pH of 7.0.

Furthermore, Fig. 5 illustrates the SEM image of the sludge produced in the batch

and continuous EC process to remove zinc from rinse water

SEM image of the sludge produced in the batch and continuous EC process to

remove zinc from rinse water

Ganesan et al. [38] once used an electrolyte cell consisting of a 1.0-L Plexiglas

vessel with magnesium as the anode and four stainless steel (commercial grade)

sheets of the same size as a cathode. In all the experiments 2 mg L–1 of Mg was

used. The optimal removal efficiency of 97.2% was achieved at a current density

0.05Adm–2 at pH 7.0. An experiment conducted by Mansoorian et al. showed that

electro coagulation can effectively reduce high amounts of metal ions with

hydroxide iron and steel flocs as absorbents. In this study, an electrochemical cell
with thirty iron and stainless steel rods with 50mm length and 5mm diameter was

used. The electrodes were connected serially and only the two outer ones had

contact to the positive and negative poles. The results showed that at current

densities of 6 and 8mA cm–3, optimum lead removal was 96.7 and 95.2 %,

respectively. At the same current densities, optimum zinc removal was 93.8% and

93.3 %, respectively. It was showed that the removal efficiency increases with an

increase in current density due to the increasing formation rate of hydroxide and

steel flocs.

EC is known as an environment-friendly technique because it uses electrons as

reagents that are clean and eliminate the need of adding new chemical additives.

Since there is no need of chemical additives, the possibility of formation of further

pollutants and generation of flocs is largely reduced. Note that EC cannot remove

infinitely soluble particles, but is has the advantage of removing even small

colloidal particles because the applied electric field sets them into faster motion.

Tab. 2 shows the removal efficiency and energy consumption that are influenced

by some parameters such as metal’s concentration, type of electrode, pH, etc.

Electro-Floatation

Electro flotation (EF) has recently been applied to wastewater to remove heavy

metal pollutants since other methods for treating wastewaters usually do not

operate efficiently for very dilute solutions (concentrations below 50 mgm–3).

Elmore reported the very first usage of EF in mineral ores in 1904. EF became

popular because of its adaptability, simplicity in design and operation,

environmental compatibility, low running costs, and its small and compact units.

Because of its various features, EF can be used in a wide range of industries, e.g.,

treating oil from oil-water emulsions, groundwater disinfection, apple juice and

food processing effluents, colloidal and suspended particles, swage water and pit

waters.

EF separates pollutants by floating them to the surface of the liquid phase. The

separation occurs through three basic parts. First, pollutants are attracted to a cell

or reactor that has two electrodes and a power supply. The overall reaction

happening in the cell will be water electrolysis that releases oxygen and hydrogen

into the solution:

2H2O2 ---›O2 +2H2 -------------------------------------- (4)

Heavy metals will adhere or adsorb on the oxygen and hydrogen molecules

whereby the emulsified particles will be destabilized and flocs will be formed. The

second step is a separation for settling or flotation of generated foam and settled

flocs. The third step is removing collected pollutants by filtration methods. The

performance of an EF cell is evaluated by the pollutant removal efficiency and the

power consumption, where the pollutant removal efficiency is dependent on the

size of the bubbles formed during electrolysis and the power consumption

depending on the cell design ,electrode materials as well as the

To overcome the limitations of the processes mentioned above, some investigators

combined EC and EF, so it leads to higher removal efficiency compared with using

one alone. This combined method is a more safe and effective way to remove

pollutants. The combination of EC and EF is called electro coagulation- flotation

(ECF). This method reaches better removal percentages. Different experiments

were carried out to investigate the effects of the operating conditions on the

removal of heavy metals. Da Mota et al. used ECF to remove heavy metals from

synthetic solutions. The experimental results revealed that it was feasible to

remove up to 97% of the Pb and Zn by ECF with a total energy consumption of

14KWhm–3 under optimum conditions of pH = 10.0 and a current density of

350Am–2.

Electro deposition

Electro deposition is a practical and efficient method among the electrochemical

processes for the recovery of heavy metals. Electro deposition is advantageous

because no further reagents are necessary, no sludge will be produced during the

process, it is highly selective and low-cost as well. It transforms dissolved metal

ions into solid particles by deposition on ionic conductors (cathode and anode) to

protect them from corrosion. Electro deposition is a one-step clean method based
on reduction and Oxidation of heavy metal ions in a cell consisting of one anode, a

cathode, an electrolyte cell, and a current source. Heavy metals are reduced and

electroplated onto the cathode. The reaction is as follows:

Mn+ +ne- --› M ---------------------------------------------- (5)

The final size and distribution of electrodeposits depends on the nucleation of

deposits and their growth [98]. The anodes are preferred to be insoluble or inert;

otherwise they will interfere with the recovery process of heavy metals. A common

side reaction at the anodes is:

4OH- ---›O2 +2H2O +4e- --------------------------------------- (6)

Some competing reactions occur during the process. One of them is a reduction of

H+ into hydrogen gas

H+ + e- ---› ½ H2 --------------------------------------------------- (7)

The efficiency of the whole process is influenced by the initial concentration of the

waste solution, physical operational parameters such as temperature and pH and

the presence of complexing and chelating agents. Electro deposition is mainly used

because it can be applied to non-aqueous solutions or solutions containing

chelating agents as well. Either of these solutions yields better removal of a

pollutant than aqueous solutions. Conventional aqueous solutions face some

problems like the liberation of hydrogen gas molecules, low thermal stability, and

narrow electrochemical window. Therefore, sometimes non-aqueous solutions are

preferred. However, there are some technical issues in the way of

commercialization of non-aqueous solutions like low current efficiency, cell heat

balance and corrosion of cell components. Electro deposition of aqueous solutions

containing chelating agents like EDTA, NTA and citrate is another interesting

case. These chelating agents are useful because they bind with heavy metals

cations to reduce the formation of insoluble salts and increase recovery efficiency

due to producing stronger complexes with metal ions. So there will be no need of

traditional separation methods. An experiment was conducted by Wulan and

Hariyadi in a batch system using two types of electro deposition reactors

(partitioned reactor and single chamber reactor), a copper plate cathode size, a

graphite anode, and applied DC of 5V. The results showed that the partitioned

reactor performed better than the single chamber reactor with a 26.892% decrease

of the nickel concentration in catholyte, a current efficiency of 88.17 %, and a

specific energy of 5.2 kWh kg–1 nickel.